JP6444386B2 - Production of fuel and biofertilizer from biomass - Google Patents

Description

The present invention, CO ₂ and inorganic emissions by the process for producing the biological fertilizer that is specialized prepared using with other liquefied byproduct step and cyanobacteria + Jiazotorofu microorganism producing algae using CO ₂ The present invention relates to an integrated biomass liquefaction process that is substantially reduced or eliminated. The invention further relates to more effective biofertilizer preparations that are possible using the prior art and methods for simultaneously controllably increasing the chemically active carbon and nitrogen content of the soil.

  Concerns about rising oil costs and future shortages have led to increased interest in other carbonaceous energy sources such as biomass to produce useful fuels and chemicals. Biomass is an important component of a comprehensive energy strategy for using domestic resources to ensure energy self-sufficiency and at the same time reduce the overall GHG footprint of related methods. Convert such materials to liquid and gaseous fuel products, including gasoline, diesel fuel, aviation fuel and heating oil, and in some cases to other products such as lubricants, chemicals and synthetic fertilizers Various methods have been proposed for this purpose.

Numerous problems that have prevented the widespread use of these pathways use various process by-products such as CO2, charcoal and waste minerals to obtain the significantly lower thermal efficiency and beneficial effects of the prior art It includes things that cannot be done. A hydrocarbon product from all or a selected portion of the biomass having a hydrogen to carbon (H / C) ratio of approximately 1: 1 to about 2: 1, for example a fuel having a H / C ratio somewhat higher than 2: 1 The conversion to, for example, causes up to half of the carbon in the biomass to be converted to CO ₂ and exhausted to the atmosphere where it is wasted. In addition, the fact that a large amount of greenhouse gas (GHG) in the form of CO ₂ has been released into the atmosphere as waste in the conversion of biomass to useful products in the past has led to the biomass liquefied fuel (BTL) process. Many have caused problems that are questioned from an environmental point of view.

  There have been proposals to at least partially overcome the GHG problem by sequestering carbon dioxide and sequestering it back into the underground. Such a plan would be costly, further reduce process energy efficiency, require a suitable underground layer available somewhere near the conversion facility, and later into carbon dioxide into the atmosphere There are shortcomings such as concerns about leaks and the waste of energy potential of the carbon content of carbon dioxide.

  Although direct pyrolysis methods have been developed to liquefy carbonaceous materials such as biomass, these methods also produce undesirable by-products such as charcoal and minerals with limited or no value. Furthermore, none of these proposed schemes achieve the combination of thermal efficiency, low cost and substantially reduced GHG emissions that would be required to be economically and environmentally attractive. There is still an important need for an economical biomass liquefied fuel conversion process that results in reduced carbon dioxide emissions combined with efficient use of CO2, carbon and inorganic by-products.

In accordance with one aspect of the present invention, highly to produce both liquids such as high-grade fuels and chemical feedstocks and self-regenerative biofertilizers that substantially reduce or even eliminate the carbon footprint of the new integrated method. An efficient integrated biomass liquefied fuel (IBTL) method scheme has been developed. The integration process has four main processes:
1- A step of directly liquefying all or part of the biomass raw material by hydrotreating;
2- producing structured biochar and hydrogen by pyrolyzing biomass residues from the liquefaction process and optionally a portion of the biomass feedstock;
3- upgrading the liquid to produce fuel and / or chemical feedstock; and 4- using the process-generated CO2 to produce algae-based biofertilizer.

  According to an important aspect of the present invention, structured biochar produced during pyrolysis is used as a nucleating agent to promote the production of algae before liquefaction of minerals such as phosphorus, potassium and other metals. As an absorbent for extraction from a biomass feedstock or from a liquefied liquid product and / or as a carrier component of the biofertilizer of the invention. According to yet another aspect of the invention, the pyrolysis conditions are controlled to substantially optimize the utility as either an algal nucleating agent, an absorbent, or a water retention agent in the biofertilizer being produced. Controlled to produce biochar with pore size. The incorporation of biochar, which has been used as an absorbent, into biofertilizers has the great benefit of adding beneficial inorganic components such as phosphorus and potassium to the biofertilizer. Additional beneficial components from other sources can also be absorbed into the biochar used as part of the biofertilizer. The use of biochar as an absorbent controls the pore size of biochar so that water or other beneficial components are released into the soil at a roughly controlled rate, thereby providing a “sustained release” function. It has another advantage of being able to.

  Biomass raw materials may be obtained from seed crops, by-products of food crop production, agriculture, food production, edible oil, waste from local government operations, or other conventional sources and / or algae. All or part of the hydrogen required for the hydrotreating and / or upgrading process can be produced during pyrolysis or supplied by hydrogen from another source.

The conversion of process-produced CO ₂ to algae and especially cyanobacteria is preferably carried out in a closed photobioreactor (PBR), although open PBR can also be used. Some of the produced algae may be used as part of the biomass. Preferably, all or most of the algae are used to produce the biofertilizer of the present invention.

  Preferably, the biofertilizer according to the present invention further comprises nitrogen fixation and / or such as, for example, preferably Rhizobium, Azotobacter and Azospirillum, which are preferably produced separately from algae-producing PBR. Phosphate solubilized diazotroph organisms are included. The concentration and composition of such diazotroph organisms in the biofertilizer is based on the composition of the soil to which the biofertilizer is to be fertilized and the particular crop to be grown therein to provide the desired amount of nitrogen fixation for the particular application May be selected.

  After inoculation of soil with algae-based biological fertilizers, especially cyanobacteria (cyanobacteria), algae and diazotrophs can be regenerated into the soil by natural regeneration using sunlight, nitrogen from the atmosphere and CO2. Soil for further plant growth that regrows at concentrations much higher than the originally applied concentration, thereby substantially reducing or even eliminating the CO2 footprint of the entire life cycle based IBTL process Substantially increase production capacity.

The biofertilizer of the present invention is a soil inoculum cultivated from a series of microorganisms, including cyanobacteria, preferably in the soil or type of soil to which the biofertilizer is to be applied, preferably already present or similar to already existing bacteria. Is included. Biofertilizer soil fertilization can range from 1 g / 1 m ^{2 to} more than 25 g / 1 m ² depending on the type of soil and soil water content. This provides a highly leveraged effect on soil (terrestrial) carbon sequestration and greatly increases soil productivity. Starting with 1 ton of CO ₂ produced in the BTL process, the use of the biofertilizer of the present invention is based on the life cycle, with the addition of tens of tons of CO ₂ removed from the atmosphere into the treated soil. Isolation can occur.

  According to yet another aspect of the present invention, the IBTL process of the present invention can be used during periods such as cloudy days and nights when there is not enough available ambient sunlight to drive photosynthesis to produce algae, for example. The CO2 produced may be part of the PBR used to liquefy CO2 or produce cyanobacteria, for example, to liquefy CO2, or under reduced pressure in an adjacent bladder until sunlight is available May be stored by storing in Alternatively, it is also possible to illuminate the contents of the PBR during non-sunshine hours to maintain algal productivity.

An important and beneficial synergy in the IBTL process and system of the present invention that contributes substantially to its overall efficiency and economic attractiveness is that the CO2 stream produced during pyrolysis and liquefaction is highly concentrated to reduce algae. Included is the fact that NH ₃ , which is an ideal raw material for production, and is essentially produced in the upgrade process, is an important nutrient in the algae production process. When a finely divided molybdenum catalyst is used in the liquefaction process, the molybdenum catalyst can be prepared in situ from a phosphomolybdic acid (PMA) precursor. Beneficially, phosphorus can be isolated from the PMA catalyst precursor and used as a nutrient in the algae production process. Furthermore, oxygen produced in the production of algae can also be supplied to the pyrolysis system.

Beneficially maximize the use of process-produced CO ₂ to produce a large number of other reaction by-products, such as algae-based biofertilizers that incorporate charcoal and minerals In addition to the advantages of the integrated biomass liquefaction method of the present invention, the self-replicating nature of such prepared biofertilizers makes it possible to add very large additional amounts that greatly expand the total carbon sequestration capacity of the method of the present invention. Isolate atmospheric CO ₂ by terrestrial.

1 is a schematic flowchart of one embodiment of an integrated biomass liquefaction system for producing biofertilizer from algae according to the present invention. FIG. 1 shows a schematic representation of a biomass conversion system suitable for use in the illustrated embodiment of the present invention.

  Referring now to FIG. 1 of the drawings, an integrated biomass liquefaction (IBTL) method and system of the present invention, wherein biomass is converted to a liquid within a liquefaction system 101, and biomass residues from the liquefaction process and / or other Carbon-containing process waste and optionally additional biomass are pyrolyzed in pyrolysis system 103 to produce structured biochar, hydrogen, bio-oil and optionally indirect liquefaction methods such as Fischer Tropsch. A preferred embodiment in which synthesis gas for synthesis or methanol synthesis (not shown) is produced is illustrated. Biomass feedstocks may be obtained from seed crops, by-products in edible crop production, agriculture, food production, edible oil, waste from local government operations or other conventional sources and / or algae. The pyrolysis system 103 when operated with co-supplied water or oxygen, or the hydrogen production system of the integrated IBTL process further preferably produces algae, and in particular cyanobacteria (cyanophyceae) through photosynthesis. A large amount of concentrated pure CO2 fed to an algae production system 105 that includes one or more sealed photobioreactors (PBR).

  The biomass feedstock to the liquefaction system 101 is: (a) raw biomass from which most of the H2O has been removed, (b) biomass remaining extracted from the raw biomass and fed to the pyrolysis system 103 after triglyceride extraction Or a fatty acid methyl ester produced by the step of transesterifying the triglyceride. The specificity of the feedstock will determine the total stoichiometric amount of hydrogen required to achieve the desired hydrocarbon production in the liquefaction process.

Removing the undesired components of the biomass feedstock prior to liquefaction by first extracting the lipid and then converting the lipid to fatty acid methyl ester is less use of H ₂ and product selection in the liquefaction process Has the advantage of allowing the ability to achieve better control of sex. Preferably, inorganics in the biomass feedstock, such as potassium, phosphorus and other metals, are also either from the feedstock prior to liquefaction or from the liquid product by absorption, for example by a bio coal bed as produced by the pyrolysis system 103. Removed.

  The produced cyanobacteria are the main components of the biological fertilizer composition of the present invention. Preferably, nitrogen-fixed diazotroph organisms are also a component of the biofertilizer composition. A portion of the produced algae may optionally be used as an additional ingredient to the liquefaction system 101 and / or the pyrolysis system 103.

  Structured biochar produced in the pyrolysis system 103 can contain phosphorus, potassium and other metals in the biomass feedstock or liquefaction system 101 to provide a nucleation site for producing algae in the PBR system 105. The organism of the present invention acts as an absorbent for removing liquids produced in and as a nutrient for the absorbed minerals and other absorbed substances in biochar to impart beneficial properties to the biofertilizer Used as a fertilizer component. Structured biochar is, for example, a substantial degree of control of its macro- and micro-pore structure so that the pore structure generated in bio-char has a roughly controlled pore size and length. It means biochar produced by a method such as microwave pyrolysis.

Bio-oils from the liquid and pyrolysis system 103 produced in the liquefaction system 101 are product separations in which they are upgraded to produce higher grade fuels such as gasoline, diesel and jet fuel and / or chemical feedstock. And supplied to the upgrading system 107. The upgrading system 107 also produces NH _{3 which} is also supplied as a nutrient to the algae production system 105. Phosphorus can also be recovered from the PMA catalyst precursor if the liquefaction system incorporates the use of a molybdenum catalyst. Optionally, as an alternative, the additional natural gas feedstock is steam methane reforming (SMR) to produce additional hydrogen for liquefaction and upgrading processes, and synthesis gas for indirect liquefaction. May be reacted.

  Catalysts useful in the liquefaction process include those disclosed in US Pat. Nos. 4,077,867, 4,196,072, and 4,561,964, which are hereby incorporated by reference in their entirety. . Suitable pyrolysis processes and reactor systems for use in the system of the present invention are described in US Patent Application Publication Nos. 2012/0237994 and 2008/0264771, which are hereby incorporated by reference in their entirety. It is disclosed in the specification.

  An exemplary embodiment of a reactor system suitable for performing biomass liquefaction according to the present invention is shown in FIG. 2 of the drawings. The biomass material is dried and squeezed in a conventional gas sweeping roller mill 201 to a moisture content of 1 to 4%. The pressed and dried biomass is then fed into a mixing tank 203 that is optionally mixed with a carrier solvent containing a regenerated bottom and optionally a liquefied catalyst precursor to form slurry vapor.

  Typical operating temperatures range from 250 to 600 ° F and more preferably from 300 to 450 ° F. The slurry is delivered to the slurry pump 205 from the slurry mixing tank. Appropriate mixing conditions are selected based on experimental studies that quantify the rheological properties of the particular slurry blend being processed.

  The slurry leaves the mixing tank 203 at about 300-500 ° F. (139-260 ° C.). Most of the moisture in the biomass is driven out of the mixing tank because of the high temperature recycle solvent (650 / 1,000 ° F. or 353/538 ° C.) and the bottom being fed into the mixing tank. Such moisture and entrained volatiles are condensed as acidic wastewater (not shown in FIG. 2). Biomass in the slurry leaving the mixing tank 203 has about 0.1-1.0% moisture. The biomass slurry is pumped out of the mixing tank 203 and the pressure is raised to a desired level by the slurry pumping system 205. The resulting high pressure slurry is optionally mixed with hydrogen and preheated in a heat exchanger (not shown) and then heated in a furnace 207.

The biomass slurry (and optionally the hydrogen mixture) is fed to the first stage input of series connected liquefaction reactors 209, 211 and 213 at about 600-700 ° F (343 ° C) and 2,000-3,000 psig ( 138-206 kg / cm ² g). Reactors 209, 211 and 213 are upward flow tubular vessels, and the total length of the three reactors is 50-150 feet. The temperature rises from one reactor stage to the next as a result of various exothermic reactions. Additional hydrogen is preferably injected between the reactor stages to maintain the maximum temperature below about 850-900 ° F. (454-482 ° C.) in each stage. The hydrogen partial pressure in each stage is preferably maintained at least about 1,000 to 2,000 psig (69 to 138 kg / cm ² g).

The effluent from the last stage of the liquefaction reactor is separated into a gas stream and a liquid / solid stream, and the liquid / solid stream is reduced in pressure within the separation and cooling system 215. The gas stream is cooled to condense and remove naphtha, distillate and solvent liquid vapors. The residual gas is then processed to remove H ₂ S and CO ₂ .

  The majority of the process gas is then sent to the hydrogen recovery system 217 for subsequent processing by conventional means for recovering the hydrogen contained therein, and the recovered hydrogen is then mixed with the biomass slurry. To be reused. The remaining portion of the process gas is purged to prevent light fraction accumulation in the recirculation loop. The hydrogen recovered therefrom is used in a downstream hydroprocessing upgrade system.

The reduced liquid / solid stream and hydrocarbons condensed during gas cooling are sent to an air rectification column 219 where they are separated into light, naphtha, distillation and bottom fractions. Light fraction is treated to recover hydrogen and C ₁ -C ₄ hydrocarbon can be used to fuel gas and other purposes. Naphtha is hydrotreated to saturate diolefins and other reactive hydrocarbon compounds. Naphtha's 160 ° F + fraction can be hydroprocessed to produce electricity to produce gasoline. When the distillation fraction is hydrotreated, products such as diesel and jet fuel can be produced.

  The air rectification column 219 is preferably recirculated to the slurry mixing tank 203 without pumping to use a portion of the bottom fraction of 600-700 ° F + (315-371 ° C. +) as solvent. Operated at a sufficiently high pressure.

  The residual bottom produced from the air rectification column 219 is fed to the vacuum rectification column 221 where it is separated into a 1,000 ° F. fraction and a 1,000 ° F. + fraction. The 1,000 ° F. fraction is added to the solvent stream that is recycled to the slurry mixing tank 203.

  The 1,000 ° F. + fraction is fed to the bottom pyrolysis system 223, where 320 to 320 hours over a period of 5 minutes to 3 hours or more to convert the reaction contents to biochar, biooil, H2, CO2 and CO. Heat to a temperature of 750 ° C. in a closed reactor under controlled atmosphere. The pyrolysis atmosphere can contain controlled concentrations of oxygen and steam. If the atmosphere is essentially free of steam or oxygen, the production of bioliquid and biochar is maximized. As the amount of steam and O 2 increases, the amount of H 2, CO 2, and CO produced by the pyrolysis system 223 will increase and the amount of bio-liquid and bio-char produced will decrease. If additional hydrogen is required for biomass liquefaction and its product upgrade, a portion of the biomass from the gas sweep roller mill 201 is pyrolyzed to produce the additional required hydrogen. 223. Biochar produced in the pyrolysis system 223 is used as an algal nucleation agent in the photobioreactor 105, as an absorbent for removing metals from biomass prior to liquefaction, and as a component in the final biofertilizer it can.

  A method for upgrading the liquid products of liquefaction system 101 and pyrolysis system 103 is disclosed in US Pat. No. 5,198099, the disclosure of which is hereby incorporated by reference in its entirety. Other methods and systems suitable for upgrading the liquid product of the liquefaction system 101 and pyrolysis system 103 are commercially available from suppliers such as, for example, Haldor Topsoe, UOP, Axens, Criterion.

The gas from the pyrolysis system 223 containing H ₂ S, CO 2 and H ₂ is then sent to a separation system such as, for example, Rectisol or Selexol. One important advantage of Selexol is that Selexol produces CO2 at a higher pressure than a scrubbing process such as MEA. This reduces the amount of compression required to store CO2 or to transport CO2 to the algae production system 111. Once hydrolyzed, H ₂ S and COS are removed, for example, by dissolution in an organic solvent or reaction with an organic solvent, and converted to a high value by-product such as elemental sulfur or sulfuric acid. UOP and other companies have licenses for the Selexol process.

Fischer-Tropsch (FT) synthesis Reactors, catalysts and conditions for carrying out FT synthesis are well known to those skilled in the art, and in many patents and other publications, for example, their contents are hereby incorporated by reference in their entirety. U.S. Pat. Nos. 7,198,845, 6,942,839, 6,315,891, 5,981,608 and Reissue Patent RE39073, which are incorporated herein. FT synthesis uses various catalysts in a fixed bed, moving bed, fluidized bed, ebullated bed or slurry reactor and uses various operating conditions that are selected based on the desired set of products and other factors. Can be implemented. Typical FT synthesis product, generally include paraffins and olefins represented by formula nCH _2. Productivity and selectivity for a given product stream is determined by reaction conditions including but not limited to reactor type, temperature, pressure, porosity, catalyst type and synthesis gas composition.

The stoichiometric synthesis gas H ₂ / CO ratio for FT synthesis is about 2.0. The ratio of _H 2 / CO in the synthesis gas produced from biomass is less than 2, and typically up to about 0.5-1.0. This ratio can be increased by mixing biomass-producing syngas with syngas produced from light hydrocarbons or natural gas. Such mixing step can not increase appropriately H _{2 /} CO ratio, and if the additional hydrogen can not be conveniently available from other available sources, such ratio of water - brought further increased by gas shift reaction It's okay. In the case of FT synthesis conversion carried out using a cobalt-based catalyst that does not promote the water-gas shift reaction, the H ₂ / CO ratio of the biomass production synthesis gas is determined by, for example, hydrogen produced by the synthesis gas production system 109, It is preferably about 2.0 before being introduced into the FT synthesis reactor. If the FT synthesis conversion that induces the water-gas shift reaction is carried out using an iron-based catalyst, it is not necessary to use a separate shift converter. However in any case, water - gas shift reaction to produce additional CO _2.

Hydrodeoxygenation Reaction When the feed to liquefaction system 101 consists entirely of lipids extracted from biomass, such as algae and / or other biomass sources, liquefaction system 101 or catalytic hydrodeoxygenation reaction and isomerization ( CHI) system or similar systems, such as WO 2009/025663, 2009/025635, 2008/8124607 or US patents, the contents of which are hereby incorporated by reference herein in their entirety. It can also be implemented using the system disclosed in US Pat. No. 4,992,605.

Capture and reuse of CO2 As mentioned above, CO2 produced by the method of the present invention is captured and used to produce algae in PBR. PBR systems can include closed or open reactor systems; closed systems allow for maximum production of specifically selected algae strains so that water loss and from external sources It is preferred to minimize contamination of the algae strain and to allow capture of oxygen produced in the algae production process for use in other combustion or pyrolysis related processes in the entire IBTL process. There are a number of commercially available algae production systems. Exemplary closed PBR systems are described in U.S. Patent Application Nos. 2007/0048848, 2007/0048859, 2012/0107921, which are hereby incorporated by reference in their entirety. It is described in the specification of 2013/0273630 and 2008/0160591. Preferably, structured biochar is added to absorb nutrients from the saline solution in the PBR to act as a nucleation site for the algae produced and from the saline contained in the biofertilizer product. Biochar in PBR promotes algae “adhesion growth” that induces algae to regenerate better in PBR and makes it easier to separate algae from saline in subsequent processing Has been found. The nutrients absorbed in the structured biochar also support the regeneration of algae and diazotroph organisms in the biofertilizer after further application to the soil.

  Algae produced in PBR are isolated in a water stream for use as a soil treatment material to increase the carbon content of the soil and to induce photosynthesis to produce additional algae in the soil it can. The diazotroph organism is preferably added to the algae either before or after the algae are dried. The resulting organism is then preferably combined with additives, such as organic binder, pyrolysis system 103 and / or alkali-containing residue from liquefaction system 101, and the final mixture is used as a natural biological fertilizer. In this capacity, this material not only causes the growth of algae and diazotroph organisms by photosynthesis in the soil, thereby increasing its natural carbon content, but also various forms of algae, in particular cyanobacteria ( Cyanobacteria) and other diazotroph organisms promote plant growth in soils that have been treated in their entirety, immobilize GHG that is the footprint of the IBTL method of the present invention, and in particular nitrogen that greatly reduces CO2. It also triggers. The diazotroph organism is preferably produced separately from the PBR for algae growth in an unknown type of bioreactor such as an autoclave. In this method, the natural complement of microorganisms, including cyanobacteria that occur in the soil or in the soil type to which biofertilizer is applied, or a similar series of microorganisms, is optimized and propagated and the resulting material Is dehydrated and dried and treated with the desired additives; then granulated and optionally coated with a material to optimize diffusivity, should be fertilized or restored Distributed on the soil.

In addition to the beneficial reduction of the GHG footprint of the IBTL system of the present invention by terrestrial sequestration of CO ₂ consumed by algae in the production of biofertilizers, the integrated system of the present invention is specifically manufactured by the present invention. In the case of biological fertilizers, algae and other photosynthetic microorganisms grow in soil through which photofertilizers are specifically applied to biofertilizers, thereby extracting more CO ₂ from the atmosphere and fixing atmospheric nitrogen It has the additional extremely important beneficial feature of being adapted to the soil because it has been selected to fit. This feature results in a net CO2 increase to a factor of 30 or more and potentially 150 times higher compared to the CO2 consumed during the production of algae in the IBTL process of the present invention, thereby increasing soil productivity. Increase greatly.

Quality of natural biological fertilizer (affected by the purity and other nutrients of the quality and CO ₂ water provided from other processes to PBR in IBTL method of the present invention), to enhance the growth of a variety of food crops Food grade / FDA certified materials for use in the environment; moderate materials to serve as soil amendments for regenerating dryland soils to prevent or inhibit wind erosion by forming bioactive crust; or biological reactions Can be controlled to produce low-purity materials for use in reclaiming used mine soil in case of contaminated soil leaching and erosion inhibition to improve the quality of discharged water . The added biochar component (described below) can be applied to further control the overall hydrophilicity and hydrophobicity of the biofertilizer preparation to further control the water retention properties of the soil. This mechanism allows the biofertilizer preparation to be tailored for optimal use in the manufacture of specific crops.

Natural biological fertilizers can be used as a direct replacement for conventional ammonia-based biological fertilizers, where the biological fertilizers are otherwise made of NH ₃ and all types of ammonia-based biological fertilizers Offsets the larger amount of CO ₂ that would be produced in This further results in other downstream effects such as a reduction in the efflux of NH ₃ -based components that contaminate downstream waterways and induce undesirable anomalies in algae and other aquatic plants.

Biofertilizer Preparations The present invention further provides specific organisms composed of various blends of process streams from the IBTL flow scheme, cyanobacteria and preferably other diazotroph organisms, biochar, and inorganic residues from pyrolysis processes. Provide fertilizer preparation. Biofertilizer preparation is a method in which elemental composition, total nitrogen level, total average surface area of the composition, surface area of individual biochar components or mixtures thereof, total alkali and individual alkali components are adjusted for a particular crop or end use Allows to be controlled by.

  In the production of a preferred biofertilizer, the PBR has a biological culture that can be removed from normal residence in the central 1 centimeter of healthy undisturbed soil with similar soil and environmental characteristics to the soil to which the biofertilizer is applied. Or a biological culture containing one or more cyanobacterial strains and preferably other photosynthetic microorganisms suitable for use as fertilizers where biofertilizers are to be used. In effect, these soil microorganisms adhere to soil particles in place, thereby limiting wind and water erosion, and providing a biological soil film that serves a number of functions including providing fertilization and plant vitality (" BSC "). Cyanobacteria and “Cyanobacteria lichens” are the main sources of fixed atmospheric nitrogen in dry ecosystems.

  Studies in the western United States observe 5-49 cyanobacterial taxa depending on the location of the study. The genus Nostock, Schizothrix, Anabaena, and Tolypothrix are the most frequently encountered heterologous cell genera. Microcoleus and Formidium are commonly encountered non-heterogeneous cell genera. In western Colorado, for example, the genus Scytonema, a heterogeneous cell genus, is frequently observed. Heterologous cells are differentiated specific cells that are responsible for nitrogen fixation. Heterogeneous cells lack the water-degradable O2-generating photosystem II device. This adaptation has evolved to eliminate inhibition of nitrogenase activity by O2, but still generates ATP energy by retaining photosystem I activity.

  Many non-heterologous cyanobacteria are known to contain nitrogenase and may fix nitrogen in the dark under microaerobic or anaerobic conditions. Microcoleus vaginalus is a very important short-lived crust component based on frequency and morphology. Microcoleus vaginalus mucosal putamenous filaments bind sand particles where they reduce erosion to produce a stable substrate for colonization of cyanobacterial lichens and other microorganisms Especially highly effective. Microcoleus vaginatus cannot immobilize nitrogen directly, but its osteogenic sheath is thought to provide a carbon source for anaerobic microenvironments and epiphytic diazotrophic bacteria.

Cyanobacteria lichens are also a major incentive for fixed nitrogen and short-lived crust cover in desert ecosystems. Lichen is a symbiosis between fungi (mycobiot) and algae (phycobionto). In most cases, the lichen phycobiot is a green algae, usually Trebuxia, but the cyanobacterium phycobionte is a cyanobacteria, most commonly Nostoc, Scytonema or Anabena. It consists of a genus (Anabaena). These cyanobacteria lichens are characteristically black, the texture is sticky and not stratified. For example, certain stratified lichens that inhabit subalpine communities such as Peltigera and Lobaria are both green Treboxia and Nostoc, a nitrogen-fixing cyanobacterium. Containing. For example, dry US cyanobacterium lichen can account for 40-100% of the ground cover and contributes significantly to soil stabilization and N ₂ fixation. Depending on the soil and abiotic environment, up to 159 lichen species representing 53 genera have been observed. Some of the most commonly encountered genera include Collema, Placinthium, Leptogium, and Heppia.

  The genus Cyanobacteria to be exploited may be obtained from biological soil membranes and include the following genera: Nostock, Anabaena, Scytonema, Tolypothrix, Calothrix, Microcoleus, Livularia, Formidium, Symproca, Schizothrix, Stigonem, Stignemect ) And Chlorococcus, but are not limited thereto. In addition to these cyanobacteria, it may be desirable to include eukaryotic algae such as, for example, Chlamydomonas, Trebouxia, and Scenedesmus. Furthermore, it is also desirable to include free-living nitrogen-fixing bacteria such as, for example, Azotobacter, Rhodospirillium or Rhodopseudomonas. Various actinomycetes, including other important soil bacteria such as Arthrobacter and Francia, Nocardia, Streptomyces and Micromonospor It may also be included to enhance nutrient cycling. Finally, it may be desirable to include lichens, saprophytes and mycorrhizal fungi to complete the microbial components of the basic photosynthetic biofertilizer. These heterotrophic microorganisms will be produced using standard methods.

  The biofertilizer is preferably designed to behave as a corrosion control agent in addition to providing soil nitrogen and carbon. In the majority of cases, biofertilizer alone will achieve the desired result. Based on biofertilizer flexibility, it can be used in conjunction with traditional erosion control methods such as fibrous root cover and tackifiers, where it enhances the effectiveness of these traditional products. For example, hard rock mine waste, waste and topsoil are characteristically acidic (pH <3) through the oxidation of sulfur by bacteria. These acidic environments inhibit seed germination and exceed the pH lower limit (pH <5) of cyanobacteria. However, when a root cover layer is applied to the surface, it has proven to serve as a chemical isolate that allows seed germination and growth of biofertilizer. Plant roots penetrate into nitrogen-deficient acidic steel scrap and continue to grow when nitrogen is supplied by biofertilizer.

  Rhizobacteria have been found to be an important component of microorganisms found in soil. Cyanobacteria, especially when present in combination with rhizosphere bacteria, act as plant stimulators, where minerals, which are important stimulators for plant growth, dissolve in the soil so that plants can access them. It is believed to produce organic acids including gibberellic acid and acetic acid as well as other mono- and polycarboxylic acids that help to do this. In addition, various types of soil formation have been found to have various complements of natural microorganisms that contribute to soil productivity for various crops and natural plant species to grow rooted. For example, Desert Institute of the Academy of Sciences, in desert soils, the main surface layer microorganisms in the sand are Fragilaria, Oscilatoria Willie, and Oscilatoria Willie I found out that it was found to be a formium okeniii). In places where the surface layer is the algal crust, the main microorganisms were found to be Synechococcus parvus, Tychonema granatum, and Formidium retzli. In places where the surface layer is a lichen crust, the main microorganisms were found to be Oscillatoria willi, Oscillatoria carbonicophila and Formidium retzli. In the case of the moss crust surface layer, the main microorganisms were found to be Synechococcus parvus, Synechocystis pavarekii and Formidium retzli. It is particularly beneficial to grow such natural colonies to form, especially in dry areas, the restoration of natural flora can stabilize and stabilize the soil as it is supplemented with carbon and other nutrients. It may be beneficial for increased production of natural plant colonies. The laboratory reports that certain species of these microorganisms are prevalent in soil samples in the Gobi Desert and neighboring deserts in China, and these species are incorporated into the final biofertilizer preparation of the present invention. It is of particular interest as a potential member of a biological population. For example, Yanmei Liu et al. A recent report by The Effects of Soil Crusts on Soil Nematode Communities Following Dune Stabilization in the Tengender Desert, North Chile, April 20th.

  Many of the microorganisms in BSC are also photosynthetic, drawing energy from sunlight so that they can produce and provide nutrients and fixed nitrogen in turn to population microorganisms that are not photosynthetic and are found deeper in the soil. The action of the BSC and the deeper population microbes that supply it work together to stabilize the soil and, over time, extract the nutrients available from the plant from the soil particles into the soil matrix. Importantly, the predominant cyanobacterial component of BSC fixes carbon and nitrogen from the atmosphere. Beginning with BSC, the combined action of these microorganisms creates conditions that benefit colonization and growth of vascular plants such as grass, shrubs and crops. In effect, BSC is a natural, solar-powered biofertilizer that inhabits the bare surface that makes it suitable and beneficial for the establishment of vascular plants over time. However, because BSC microorganisms multiply slowly in dry climates and are not very mobile, physical disturbances such as farming, livestock stocking and fires can stop the beneficial effects of BSC for soil and BSC. Moreover, these benefits can take decades or hundreds of years to recover naturally in dry climates.

  The preferred biofertilizer production rapidly regenerates native selective BSC microorganisms in PBR on an industrial scale. Microorganisms then constitute preferred biofertilizers and are spread on land that currently lacks healthy soil crust colonies, where they form “inoculated seeds” for these microorganisms that promote the natural recovery of the soil To be mixed carefully. As biological fertilizer grows on the soil surface, it draws more and more carbon from the atmospheric CO2 into the soil, where it becomes part of a living, sustainable microbial community, Isolate effectively. Through soil inoculation with the preferred biofertilizer, natural growth on the soil and enhancement of secondary vascular plant growth, conversion from 1 ton of CO2 to the next preferred biofertilizer applied on the appropriate soil is: Through direct photosynthetic uptake of atmospheric gases, a reduction in CO2 from the atmosphere of up to 50 tons can be achieved each year.

  The cyanobacteria and their soil consortium used to produce biofertilizers are preferably US 2008/0236227 to Flynn, the contents of which are hereby incorporated by reference in their entirety. (Hereinafter referred to as "Flynn") in the inoculum and used to inoculate the PBR for growth also taught by Flynn, where the culture is It can grow rapidly in liquid media with easy access to nutrients, carbon dioxide, sunlight and hydraulic mixing. PBR may be supplemented with a carbon source that is sunlight, nutrients and most commonly carbon dioxide, but may be in a fixed form such as sodium bicarbonate or other bioavailable form.

A preferred method for producing a biofertilizer according to the present invention is as follows:
(1) isolating photosynthetic biological soil microbes that are important for producing multicultural cultures that closely reflect the composition of the natural microbial species;
(2) culturing the culture in PBR, preferably under controlled conditions designed to maximize biomass productivity;
(3) harvesting the produced biomass, for example by simple gravity driven sedimentation and filtration, purification or centrifugation;
(4) preferably adding separately produced diazotrophic microorganisms to the biomass;
(5) storing the biomass by, for example, reflexance-window drying techniques, or other methods such as, for example, air drying, spray drying, vacuum drying, or freezing such that the cells remain viable; 6) including crushing, chopping or pulverizing dry cyanobacteria and diazotrophic microorganisms to facilitate packaging, storage, transport and final application of biofertilizer.

  After growing in PBR, soil microorganisms are captured, preferably mixed with diazotroph microorganisms, and mixed using a mixture and coating to create a product biofertilizer. Biological fertilizers can be fertilized on farmland or damaged land using standard farming practices such as pesticide application, mixing with irrigation water or fertilization using a spreader. Once placed on the soil surface, the natural availability of carbon dioxide and nitrogen in the air, along with available shared or irrigation water and sunlight, is the condition of growth for biofertilizers for specific communities of microorganisms. Induces the induction of colony growth of soil microorganisms in proportion to fitness.

The microbial community in the locally adapted biofertilizer preferably represents the non-biological composition to the soil in the area to be treated, which represents the best and best desired microbiological outcome for the treated soil And derived from desired target outcome soil patches that are similar in environmental factors. In this way, the microbial community is unique to produce a specific area type of biofertilizer that contains the most preferred microorganisms to survive, grow and fertilize on the targeted soil to be treated in that area. Can be selected. If this is done and the biofertilizer is sprayed to a sufficient surface density, then the crust will re-establish at an accelerated rate clearly preceding natural growth. In farmland development activities, sufficient application density is approximately 0.1 to ² biofertilizer particles per cm ² (square centimeter). In agricultural applications where accelerated fertilization capability is required, sufficient application density is the number of organisms fertilizer particles is approximately 1 to 20 per 1 cm ^2.

As microorganisms grow and proliferate in and on soil, uptake of CO2 from the atmosphere can further increase population size, impact light, water availability, soil type, and net primary productivity of soil It increases in proportion to the occurrence of secondary vascular plant growth. The amount of CO2 depleted from the atmosphere will vary widely depending on these factors. When the crust is grown to maturity in the land improvement applications it is estimated of CO2 per year 1 m 2 ^(square meter) per about 100g to decrease from the atmosphere.

  The purpose of the inoculum PBR is to obtain organisms from the target outcome soil and initiate the growth of population replication in PBR liquid media. The population produced by the inoculated PBR has substantially the same or otherwise sufficient microbial symbiotic members, and the same or otherwise sufficient equilibrium as if it were present substantially naturally in the soil. Had to have. PBR operators use input and output populations and growth media assay data to influence, for example, light, pH, temperature, CO2 and nutrient levels and desired growth rates and population equilibrium characteristics to incubator outputs Adjust growth input parameters such as mixing speed. In a similar manner, the incubator and production PBR operators look at the population between the PBR input and output and the growth media assay results and adjust the same growth conditions to achieve the desired results. In some cases, the desired product population ratio may differ from the ratio found in the target outcome soil, but the difference will give better results after application.

  The pH and rate of photosynthesis in the PBR system can be measured using a controller, capture software, dissolved oxygen, pH and temperature probes available from Point Four Systems (Richmond, British Columbia Canada). The difference in dissolved oxygen between the lower and upper probe arrays provides a measure of photosynthesis. Similarly, the difference in pH between the lower and upper probe arrays is a measure of CO2 consumption. Under illumination, the microorganisms will synthesize and absorb CO2, causing an increase in the pH of the medium. When the pH rises to a selected set point, preferably pH 7.5, the controller introduces 100% CO2 into the PBR, which induces a pH drop as a result of the formation of carbonic acid and related complexes. become.

  The output of the PBR may be fed into a filtration and drying belt into which various optional mixtures can be applied. The resulting dried flake and its optional coating may then be granulated to become a biofertilizer. The final biofertilizer product can be distributed and fertilized to the soil by various agricultural and land improvement spreaders. Beneficially, the biofertilizer pellets can be spread by a rotary spreader or airplane so that they are not blown away by the surrounding wind. Biofertilizer can also be mixed with irrigation water and sprayed onto crops.

  The various mixtures that can optionally be included remain more physically related, preferably in the same relative proportions as the microbial community, even when the composite mixture / biomass flakes are reduced in size by granulation. It is. By stratifying uniformly as the flakes are produced and injecting the mixture homogeneously throughout the flakes, these relative ratios of the mixture / biomass can then be maintained during the granulation and particle coating process. The dry mix components may also be added as the biomass mat begins to solidify, but this serves to mechanically integrate them with the biomass by incorporating a portion of the dry mix within the filaments of the integrated cyanobacteria . A wet mixture is typically, but not exclusively, a dry protectant and a sugar-based composition of a nutritional additive that is a heterotrophic community member that functions to bind and adhere all ingredients as they dry. It is a thing. To this end, the use of actual mucus or other water-soluble adhesives or solvent-based but UV-degradable binders can also be considered for this purpose.

The following are optional mixtures and their purposes:
1) Antioxidants, such as β-carotene, can protect biological fertilizers during the drying process and during storage.
2) Trehalose, called dry protectants, such as sucrose and other sugars, or biologically derived dry protectants, can prevent cell damage from rapid drying and prolonged drying over time.
3) Growth nutrients include the micronutrients required by all soil microorganisms taught by Flynn, including sugar for feeding to the non-photosynthetic cohort during the early stages of establishment.
4) Sand or clay fillers serve two purposes. One is to increase the weight density of the resulting granular particles, thereby making them more aerodynamically dispersible and resistant to airflow from airplanes and ground based spreaders. Another object is to provide an undamaged site for break lines between microorganisms dried during granulation that do not split the microorganisms themselves.
5) The spray pattern tracer may be a fluorescent additive. Another tracing tag may be the use of a unique but non-operating unique gene sequence of one of the microorganisms that grows at the same rate and spatial characteristics as the biological fertilizer propagates. This allows researchers or carbon credit inspectors to visit a section of soil months or years after the first application of biofertilizer, and how much soil film or subsurface biomass is specifically tagged. You will know if it is directly attributable to the growth and beneficial effects of the fertilizer.
6) Vascular plant seeds such as restoration grass or actual crop seeds may be part of the mixture. In this case, the biofertilizer will be designed to work in biological agreement with the embedded vascular plant seed to achieve and maximize the desired recovery of the fertilization result.
7) A tackifier may be added to the mixture to quickly combine the particles with other soil particles once wetted in the environment to prevent further migration by wind or water erosion.
8) Other microorganisms may be added to either the dry or wet mixture. These other microorganisms may be selected for their auxiliary properties such as being good tackifiers, or selected because they are an important part of the biological community of biofertilizers Good; yet, for various reasons such as, for example, incompatibility of the type of growth medium or susceptibility to predation, they were unable to co-grow in the same PBR with the rest of the biofertilizer community members.
9) Biochar from biomass pyrolysis is added specifically to enhance the total carbon content and to provide a powerful adsorbent for various other mineral and cyanobacterial components. This changes the overall moisture and nutrient retention capacity of the prepared biofertilizer, allowing it to be tailored to the needs of a particular crop and geographical location.
10) Oxidation of inorganic ash and resulting residue from biomass pyrolysis may be added to biofertilizers prepared to control total K delivery capacity and adjust the total pH of the soil to be treated. Here again, the level can be adjusted to the needs of a particular crop or soil treatment protocol. Other inorganic elements may be added from combustion or pyrolysis processes, particularly those operated in the biofertilizer production process and integration process of the present invention. Materials containing an alkali or alkaline earth metal with a sulfur or nitrogen containing counter ion are particularly useful. Calcium sulfate and nitrates, potassium nitrate and other nitrogen containing salts are also useful.

  The biologic may also be spray coated on the outside of the particles. In this context, “biologic” can mean any live or dead cell or bioactive substance that affects the ability of the soil to be colonized by biofertilizer microorganisms. Alternatively, these substances may be intended to prevent the consumption or destruction of biological fertilizers by other organisms such as insects, other microorganisms, birds or other humans and animals.

  A preferred method of producing structured biochar is by microwave pyrolysis which gives the representative results provided below.

  Detailed investigations on microwave pyrolysis pathways demonstrate that individual characteristics of biochar can be altered by controlling total energy input, catalyst (eg, K2CO3 or Na2CO3) charge and system operating conditions.

  Furthermore, this phenomenon is also observed when other pyrolysis temperatures are used as shown below.

  As is clear from the above, the total effective surface area of the biochar component is specifically adjusted by controlling the operating conditions in the pyrolysis process and controlling the total porosity and absorbability of the biochar component in the prepared biofertilizer Is possible. The preferred range of average pore sizes for biochar used as algal nucleation sites ranges from 20 to 400 angstroms. Biochar for use as an inorganic absorption medium preferably has an average pore size ranging from 40 to 200 kg. Biochar used as a water retention medium as a biological fertilizer component preferably has an average pore size of 20 to 400 mm, more preferably 100 to 400 mm. The biochar concentration contained in the biofertilizer composition ranges from 10-50% by weight of the final preparation.

Similarly, raw biochar from non-catalytic pyrolysis combined with biochar from a process in which specific levels of K ₂ CO ₃ or other alkali or alkaline earth oxides or salts are added to the biomass prior to pyrolysis By controlling the ratio, it is possible to vary the total surface area, the total potassium K level and the total alkali available. Biochar characteristics and exemplary methods of preparation are described in “Evaluation Of The” which was submitted to McGill University in August 2011 by Pavithra Sellaperumal in part fulfilling the requirements for obtaining a Master of Science in Bioresource Sciences. Thermochemical Decomposition of Various Lignocellulosic Biomass for Biochar Production ”.

In order to minimize the CO ₂ footprint in the system of the present invention and convert substantially all of the CO ₂ to algae, the produced CO ₂ preferably drives the CO ₂ consumption by algal biomass production. There is not enough light for photosynthesis, or it is stored during periods of microlight or dark battle. In order to further minimize the CO ₂ footprint on a life cycle basis according to the present invention, algae are then preferably used as biofertilizer according to the system described above. Combining these steps together, allowing the height equivalent of 270 times the CO ₂ conversion using the open pounds or PBR without using artificial light to algae recovery and reuse. If not stored, the amount of CO2 that is reused decreases by a factor of 2 or more. The storage technology of CO _2, the liquefaction of CO _2, conversion of CO ₂ by known conventional chemical methods to ammonium hydrosulfide or urea, and the like physical storage.

  The novel process integration of the present invention also allows for more effective use as a feedstock by-product stream from one section of the IBTL facility to another. This superior design improves the overall efficiency and reduces the total investment by 15-20%, so this allows the generation of almost double numbers per ton of biomass compared to alternative biomass liquefaction pathways. To remove significant barriers to entry.

There are several commercial systems that can be used to separate hydrogen from carbon monoxide. The pressure swing adsorption (PSA) method relies on the fact that under pressure gas tends to be attracted or “adsorbed” to the solid surface. The higher the pressure, the more gas is adsorbed; as the pressure decreases, the gas is released or desorbed. The PSA method can be used to separate gases in a gas mixture because different gases tend to be more or less strongly attracted to different solid surfaces. H2, the synthesis gas mixture of CO and CO ₂ may be separated by PSA to produce a hydrogen-rich stream. Or synthesis gas is first subjected to a water gas shift process, whereby the PSA, or other means known in the art, for example, membrane separation method (much more effective than H2 is CO ₂ in order to separate the pure hydrogen stream it is possible to produce a two-component mixture of H2 and CO ₂ that can be separated by osmotic be) to. Finally, the use of active metal membranes of palladium and other related metal alloys can separate hydrogen from other gases, creating a commercially available option. U.S. Pat. Nos. 5,792,239, 6,332,913 and 6,379,645 and U.S. Patent Application Nos. 2003/3190486 and 2009/0000408 are a variety of such separation techniques. Methods are described and are incorporated herein by reference in their entirety.

CO ₂ capture includes various conventional recovery methods including but not limited to adsorption, absorption (eg, pressure swing adsorption (PSA) and displacement purge cycle (DPC)), cryogenic separation, membrane separation, combinations thereof, and the like. Can be used. One or more recovery steps may be required to recover CO ₂ from synthesis gas or exhaust gas, but byproducts from reformers or C3 + product modifiers are easily detectable amounts of It does not contain H ₂ or H ₂ O, and there may be no need for any recovery step, except for the condensation of heavy hydrocarbons (C6 +). Further, in the method of the present invention it is desirable to use a CO ₂ recovered, it is also possible to replace the CO ₂ thus obtained was recovered CO ₂ from an alternative origin of integrated in the complexes .

  Product streams from the process of the present invention can be, for example, synthetic crude product streams and other individual product streams such as liquefied petroleum gas (C3-C4), condensate (C5-C6), high octane blend components (C6-C10). Aromatic-containing streams), jet fuels, diesel fuels, other distillate fuels, lubricant blend stocks or lubricant blend feedstocks that can be manufactured and sold as separate products.

Exemplary Biofertilizer Manufacturing Procedure A number of different bacterial strains can be beneficially used as components of biofertilizer. Exemplary methods for producing the diazotrophic organisms Rhizobium, Azotobacter and Azospirillum, except that the broth or liquid medium used is preferably different for different organisms. The following steps are included. The preferred media used for each organism is:
i) Rhizobium: yeast extract-mannitol ii) Azotobacter: Ashby medium iii) Azospirillium: Okon et al. (1977) Medium prepared by (iv) iv) Phosphate solubilized bacteria: Pikiyskaya medium.

1. Preparation of mother culture or starter culture:
Starter cultures of selected diazotroph strains are obtained after elucidating performance at the greenhouse and field levels. Pure cultures of efficient strains of nitrogen-fixing diazotroph organisms are grown on each agar medium above the slope and maintained in the laboratory. Loops filled with inoculum from each slope are transferred to Erlenmeyer flasks each containing 250 ml of the appropriate liquid medium. Erlenmeyer flasks are maintained on a rotary shaker for 3-7 days, depending on whether the organism is growing fast or slow. The contents of the flask, called mother culture or starter culture, usually reach a loading of 10 ⁵ to 10 ⁶ cells / mL. This mother culture is further grown in a larger flask.

2. Broth culture preparation:
An equal volume of appropriate liquid medium for each organism is prepared in a large Erlenmeyer flask (1,000 mL) and sterilized in an autoclave at a pressure of 15 lbs for 1/2 hour. After sterilization, each flask is aseptically inoculated with the mother culture at a ratio of 1: 5. Flask, the viable cell count per 1mL maintains a rotary shaker over 96 to 120 hours to reach 10 ⁹ cells. Broth is more concentrated and more viscous. This broth culture must not be stored for more than 24 hours at ambient temperature, or it must be maintained at a temperature of 4 ° C if stored for longer periods of time.

3. Carrier preparation:
The carrier must have the following properties:
a) High organic matter-over 60% b) Slightly soluble salt-less than 1% c) High water retention capacity-150-200%
d) Providing a nutrient medium for bacterial growth and extending survival during culture as well as on inoculated seeds.
Structured biochar is a preferred carrier and lignite or peat may also be used as a carrier in the preparation of biofertilizers. The carrier is crushed and powdered to 200-300 mesh. The peat or lignite powder is neutralized by adding 1% calcium carbonate (CaCO3) and sterilized at 15 lbs pressure in an autoclave for 3-4 hours.

4). Preparation of inoculum:
Sterilized and neutralized lignite, peat or other carrier material is mixed with a high density broth culture in a galvanized tray. About 1 part by weight broth is required for 2 parts by weight of dry carrier. The final water content varies between 40 and 50% depending on the quality of the carrier.

5). Curing or maturation:
After mixing the broth culture and carrier powder in the galvanized tray, the tray is maintained at room temperature (about 28 ° C.) for 5-10 days to cure. After curing, the contents of the tray are screened to disperse the concentrated growth pockets and disrupt the mass.

6). Filling and packing:
After curing, the screened powder is stored in a 0.5 mm thick polyethylene bag, leaving about 2/3 of the space open for air supply to the bacteria, and the bag is sealed.

7). storage:
The inoculum must be stored away from open flames, preferably in a cool place at a temperature not exceeding 15 ° C.-30 ° C. ± 2 ° C. for up to 6 months. In order for the microorganisms to survive longer, the bags must be stored cold at a temperature of 4 ° C.

Culture of microorganisms Preferred media for mass production of Rhizobium, Azospirillum, Azotobacter and Phosphobacteria are as follows.

  After adjusting the pH to 6.8 and before adding agar, add 10 mL of Congo Red stock solution (250 mg of Congo Red dissolved in 100 mL of water) to 1 L of water.

Broth is prepared in the flask and the inoculum from the mother culture is transferred to the flask. The culture is grown as a submerged culture at 30 ± 2 ° C. under osmotic conditions. The culture is incubated until a maximum cell population of 10 ¹⁰ to 10 ¹¹ cfu / mL is produced. Under optimal conditions, this population level is within 4-5 days for Rhizobium; 5-7 days for Azospirillum; 2 to 2 for Phosphobacteria. It may be achieved within 3-7 days and for 6-7 days for Azotobacter. The culture obtained in the flask is called starter culture. For large-scale production of the inoculum, the inoculum from the starter culture is transferred to a large flask / seed tank type fermentor and grown until the required number of cells is reached.

Bacterial growth in batch culture can be modeled using four different phases: induction phase (A), logarithmic or exponential growth phase (B), stationary phase (C) and death phase (D).
1. During the log phase, the bacteria are compatible with the growth conditions. The logarithmic period is a period in which individual bacteria are mature but cannot yet be divided. During the logarithmic phase of the bacterial growth cycle, synthesis of RNA, enzymes and other molecules occurs.
2. The log phase (sometimes called the logarithmic or exponential growth phase) is a period characterized by cell doubling. The number of new bacteria that appear per unit time is proportional to the current population. Under controlled conditions, cyanobacteria can double their population four times a day. However, exponential growth cannot continue indefinitely because the media will soon be depleted of nutrients and become rich in waste.
3. The stationary phase is often due to growth limiting factors such as depletion of essential nutrients and / or the formation of inhibitory products such as organic acids. The stationary phase results from conditions where the growth rate and death rate are comparable.
4). In the death phase (decay phase), the bacteria consume their nutrients and die.

The following is an exemplary procedure for preparing an algae or diazotroph bioinoculum.
Inoculate (in logarithmic phase) 500 mL, 3 L and 5 L flasks containing the appropriate medium with the corresponding starter culture or mother culture.
• Prepare a large amount of the above medium in the fermentation apparatus, sterilize and cool.
Inoculate the medium in the fermenter with log phase culture grown in 5 L flasks. Usually 1-2% inoculum is sufficient, but inoculation is carried out at up to 5% depending on the growth of the culture in larger flasks.
• Cells grow with continuous agitation by providing air supply in the fermenter (passing sterile air through a compression device and a sterilant such as glass cotton, cotton wool, acid).
• Bros checks for inoculated organisms and contaminated populations, if any, during the growth phase.
• Cells are harvested at a population load of 10 ⁹ cells / mL after the incubation period.
• There should be no fungal or other bacterial contamination at a dilution level of ^10-6 .
• It is not wise to store broth for longer than 24 hours after fermentation. Viable counts begin to decrease even at 4 ° C.

Processing of the carrier material The use of a suitable carrier material contributes to the production of excellent quality biofertilizer. Peat soil, lignite and biochar are preferred carrier materials. Vermiculite, charcoal, pressed mud, compost and soil mixtures can also be used as carriers. Neutralized peat soil and lignite have the advantages of considerably lower cost, high organic content, non-toxicity, easy to process and water retention capacity of more than 50%.
The carrier material is powdered so that it can pass through a 212μ IS sieve.
-The pH of the peat soil and lignite carrier material is neutralized with a calcium carbonate that is acidic (pH of 4-5) (ratio of 1:10).
• Sterilize the neutralized carrier material to remove contaminants in the autoclave.

Preparation of the inoculum packet • Spread the neutralized and sterilized carrier material in a clean, dry sterile metal or plastic tray.
• Add the bacterial culture removed from the fermenter to a sterile carrier and mix thoroughly. The culture suspension is added to a level of water retention capacity of 40-50% depending on the population. This concentration corresponds to an initial wetting point that can re-hold half of the bulk water and still be free-flowing.
The inoculum is packaged in a polyethylene bag in an amount of 200 g that is sealed and allowed to cure for 2-3 days at room temperature.
Polyethylene bags must be low density grade and have a thickness of about 50-75μ.

Mass production and use of mycorrhizal diazotroph biofertilizers The following is an exemplary method for producing mycorrhizal (AM) fungi:
-Grooves (1 m x 1 m x 0.3 m) are formed and lined with a black polyethylene sheet used as a plant growth tab.
Mix 50 kg vermiculite and 5 kg sterilized soil and fill in the ditch to a height of 20 cm.
Apply 1 kg of AM inoculum (mother culture) 2-5 cm below the surface of vermiculite.
-Sowing corn seeds whose surface has been sterilized with 5% sodium hypochlorite over 2 minutes.
Apply 2 g urea, 2 g lime perphosphate and 1 g potassium chloride to each groove at the time of seeding. Further, seeding each groove, 10 g of urea is applied twice after 30 days and 45 days.
• The quality test for AM colony formation in the root sample is performed on days 30 and 45.
-Growing stock plants for 60 days (8 weeks). The inoculum is obtained by cutting all the roots of the stock plant. The inoculum produced consists of a mixture of vermiculite, spores, mycelium pieces and infected root pieces.
• Within 60 days, 55 kg of AM inoculum could be generated from an area of 1 m ² . This inoculum is sufficient to treat a 550 m ² nursery area with 11,000 seedlings.

For the nursery applications, it is sufficient to use a bulk vermiculite support AM (VAM) inoculum of 1 m ² per 100 g. The inoculum must be applied 2-3 cm below the soil surface at the time of sowing. Seeds / cuts must be seeded / planted above the VAM inoculum to induce infection.

  For polyethylene raised crops: 5-10 g bulk VAM inoculum is sufficient for each packet. 10 kg inoculum is mixed with 1,000 kg sand potting mixture and the potting mixture is packed in a polyethylene bag before sowing.

  For transplantation: 20 g VAM inoculum per seedling is required. Apply the inoculum at the time of planting. ■

  For existing trees: 200 g of VAM inoculum is required to inoculate one tree. The inoculum is applied to the surface crust of the root at the time of biofertilizer application.

Cyanobacterial mass production and field application Inoculation of cyanobacteria (BGA) including complex cultures has been found to be much more effective than single culture inoculation. A technology for large-scale production of cyanobacterial complex cultures under rice field conditions has been developed, and it has been found that soil-based BGA inoculum can survive for more than two years. In many places where algal inoculation was used over 3-4 consecutive cropping seasons, the inoculated algae settled and the effect persisted over subsequent rice crops. Cyanobacterial inoculum may be produced in several ways: in tubs, in galvanized trays, in pits and in closed or open PPR in field conditions. However, large-scale manufacturing under field conditions that can be readily employed by farmers is often preferred.

I. Growth in trays • Large metal trays (6'x3'x6''lbh) can be used for small scale production.
-Take out 10kg of paddy soil and dry the powdered soil firmly and spread.
Fill with water to a height of 3 ''.
Add 250 g dry algal flakes (soil based) as inoculum.
Add 150 g of superphosphate and 30 g of lime and mix well with the soil.
Sprinkle 25g of carbofuran to control insects.
・ Maintain the water level in the tray.
• After 10-15 days, BGA flowers begin to float on the water source.
・ Stop watering at this stage and drain. Allow the soil to dry completely.
• Collect inoculum based on dry soil as flakes.
・ Store in a dry place. By this method, 5-7 kg of inoculum based on soil can be obtained.

II. Growth material under field conditions • Rice field • Superphosphate • Carbofuran • Composite BGA starter culture procedure Select a 40m2 (20m x 2m) area near the water source that is directly exposed to sunlight. A support ridge up to 15 cm in height that surrounds the entire compartment is made and coated with a non-permeable layer of plastic or dense sand to prevent water loss due to water permeability.
A small compartment was prepared firmly and evenly smoothed to a water depth of 5 to 7.5 cm and deposited for 12 hours.
Apply 2 kg of superphosphate lime and 200 g of lime evenly over the whole area in a small compartment.
-Powdered firmly with a composite starter culture based on BGA soil containing 8-10 species per 5 kg.
Carbofuran is also applied at 200 g to control soil insects that develop in BGA.
Water is injected at regular intervals so that the water level is always maintained at 5 cm.
• 15 days after inoculation, the parcels are completely dried under sunlight and the algal flakes are collected and stored. Alternatively, bubble separation or other separation means may be used to isolate BGA cells from water.
• The floating algal flask is green or turquoise. From each harvest, 30-40 kg of dry algal flakes are obtained from a small section.

III. BGA Inoculation Method in Rice Fields Cyanobacteria may be applied as soil-based inoculum for rice fields according to the method described below.
• Powdering algal flakes based on soil.
Mix it with 10 kg of soil or sand (10 kg of powdered algal flakes containing 10 kg of soil / sand).
• BGA must be inoculated 7-10 days after rice planting.
• 3-4 ″ water level must be maintained at the time of BGA inoculation and for one month thereafter to obtain the highest BGA.
-Algae growth can be seen one week after BGA inoculation and the algal mat will float on the water after 2-3 weeks. The color of the algal mat will be green or green brown or yellowish green. Individual microorganisms may be applied separately to rice fields, but usually a multi-component mixture of these microorganisms is applied in a single application using a physical mixture of cyanobacteria, diazotrophs and structured biochar. Is preferred. In this way, we eliminate the need for continuous application of individuality.

Large-scale production and field application of Azolla diazotroph organisms Azolla (Azola) floats in water and binds to the nitrogen-fixing cyanobacteria Anabena azolae (Anabaena azolae) to fix atmospheric nitrogen It is a floating aqueous fern. The leaflet of the genus Azolla consists of spores with floating rhizomes and small overlapping bilobes and roots. The genus Azola is used as a biological fertilizer for paddy rice and is known to contribute 40-60 kg of Nha-1 per rice crop. According to the present invention, Azola is a single application in combination with structured biochar and cyanobacteria as a biofertilizer with substantially improved properties compared to Azola alone, Or applied continuously.

I. Large-scale growth of Azolla under field conditions A simple Azolla breeding method has been developed for large-scale propagation of Azola in the field so that farmers can easily adopt it. ing.
Ingredients • Small section of 1 cent (40m ² ) area • Cow dung • Superphosphate lime • Huladan • Fresh Azolla inoculum procedure • Select paddy field, prepare completely and level evenly.
• Mark a 1 cent parcel (20 x 2m) by providing appropriate dikes and irrigation channels in the paddy field.
-Maintain the water level at a height of 10 cm.
・ Mix 10kg of cow dung into 20L of water and spread it in the field.
• Apply 100 g lime superphosphate as the prescribed dose.
Inoculate each pot with 8 kg of fresh Azola biomass.
Apply lime superphosphate at 100 g as the top layer biofertilizer 4 and 8 days after inoculation with Azolla.
Apply carbofuran (Furadan) at 100 g / slot 7 days after inoculation with Azola.
• Maintain the water level at a height of 10 cm throughout the 2 or 3 week growth period.
• Harvest Azolla mat floating on a small plot, drain and record biomass.

II. Methods for Inoculating Rice Crops with Azolla Azolla biofertilizers may be applied to paddy rice in a variety of ways. In the first method, fresh Azola biomass is inoculated into paddy fields and then transplanted and incorporated as green manure. This method requires a very large amount of fresh Azola. In other methods, Azola can be inoculated after rice planting, grown as a double culture with rice, and subsequently incorporated.
A. Incorporation of Azola biomass as a green manure for rice crops • Fresh Azola biomass is collected from the Azolla seedling subdivision.
• Prepare wetlands well and maintain water just enough for easy integration.
Apply fresh Azola biomass (15tha-1) to the main field and incorporate Azola using farm equipment or a tractor.
B. Inoculation of Azolla as a double crop for rice • Select rice fields planted.
-Collect fresh Azolla inoculum from Azolla nurseries.
・ Sprinkle fresh Azolla (500 kg / ha) on rice fields planted 7 days after rice planting.
-Maintain the water level at 5-7.5 cm.
• Observe growth of Azola mats 4 weeks after rice planting and incorporate Azola biomass using farm equipment or tractor or during intercultivation work.
• Secondary flowering of the genus Azolla occurs 8 weeks after rice planting, but this may be incorporated again.
• 20-25 tonnes of Azolla can be incorporated into 1 hectare rice field by two integrations. Azola may also be processed by first drying and pulverizing in a manner similar to that described above for other diazotrophs. In all cases, Azolla is combined with structured biochar and cyanobacteria in biofertilizers.

Application of biological fertilizer The biological fertilizer of the present invention may be applied either as seed treatment or seed inoculation, as a seedling dipping method, or as a main field application. For seed treatment, 1 packet of inoculum is mixed with 200 mL rice kanji to make a slurry. The seed required for one acre so that it has a uniform coating of inoculum throughout the seed is mixed into the slurry and then shaded for 30 minutes. Shaded seeds must be sown within 24 hours. One packet of inoculum (200 g) is sufficient to treat 10 kg of seed.

  The seedling dipping method is used for transplanted crops. Two packets of inoculum are mixed with 40 L of water. The seedling roots required for one acre are immersed in the mixture for 5-10 minutes and then transplanted.

  For main field applications, 4 packets of inoculum are mixed with 20 kg of dried and powdered farm compost and then sprayed into 1 acre main field just before transplanting.

Rhizobium
All legumes Rhizobium are applied as seed inoculum.

Azospirillum / Azotobacter
In crops to be transplanted, Azospirillum is inoculated through seeds, seedling dipping methods and soil application methods. For crops that are sown directly, Azospirillum is applied through seed treatment and soil application.

Phosphobacteria (Phosphobacteria)
As in the case of Azospirillum, it was inoculated through seed, seedling dipping and soil application methods. Combined use of bacterial biofertilizer. Phosphobacteria can be mixed with Azospirillum and Rhizobium. These inoculums must be mixed in equal amounts and applied as described above.

Guidelines • Bacterial inoculum should not be mixed with insecticides, fungicides, herbicides and chemical fertilizers.
• Seed treatment with bacterial inoculum must be performed at the last time the seed is treated with a fungicide.

  Phosphobacteria The recommended amount of Azospirillum is adopted for Phosphobacteria; for combined inoculation, both biofertilizers should be uniformly applied before use Must be mixed.

Claims (15)

A method for converting biomass into liquid fertilizer based on liquid fuel and cyanobacteria:
a. Directly liquefying the biomass feedstock by hydrotreating the feedstock over the conditions and sufficient time to produce a hydrocarbon liquid;
b. Upgrading the hydrocarbon liquid produced by step a and the by-product ammonia to produce liquid fuel and / or chemical feedstock;
c. Producing structured biochar and by-product CO ₂ having an average pore size in the range of 20 to 400 kg by microwave pyrolysis of the biomass residue produced in step a;
d. Producing cyanobacteria in a photobioreactor (PBR) by using by-product CO ₂ produced by one or both of the direct liquefaction and biochar production processes; and e. A method comprising producing a biofertilizer incorporating the biochar and cyanobacteria produced in steps c and d.   The method of claim 1, further comprising adding a diazotroph microorganism to the cyanobacteria for inclusion in the biofertilizer.   The method of claim 1, further comprising removing inorganics from the biomass feedstock or from the hydrocarbon liquid prior to the direct liquefaction by absorbing inorganics in biochar.   The method of claim 3, wherein structured biochar incorporated in the biofertilizer contains the absorbed inorganic matter.   Contains a combination of cyanobacteria, diazotrophic microorganisms and structured biochar with an average pore size in the range of 20-400 mm produced by microwave pyrolysis, the total carbon and active nitrogen content of the soil for a given crop A method for optimizing a process of treating such soil with a biological fertilizer, wherein the ratio of cyanobacteria to diazotroph microorganisms in the biological fertilizer is a desired total chemically active carbon in the soil. And a method selected to achieve a nitrogen content.   A biofertilizer having a composition comprising cyanobacteria, diazotrophic microorganisms and structured biochar produced by microwave pyrolysis and having an average pore size in the range of 20-400 cm.   The organism according to claim 6, further comprising one or more additional microorganisms selected from the group consisting of free-living nitrogen-fixing heterotrophic bacteria, actinomycetes, photosynthetic bacteria, mycorrhizal fungi or lichens and combinations thereof. fertilizer.   8. The nitrogen-fixing heterotrophic bacterium is selected from Azobacteriaceae or Franciaceae consisting of Azotobacter, Francia or Arthrobacter, according to claim 7. The biological fertilizer described.   8. A fertilizer according to claim 7, wherein the photosynthetic bacterium is selected from Rhodospirilles, including Rhodospirillium, Rhodopseudomonas, and Rhodobacter.   The mycorrhizal fungus belongs to the genus Glomales, and the lichen fungus belongs to the genus including one or more of the genus Collema, the genus Pertigera, the genus Psora, the genus Heppia and the genus Fulgensia, The biofertilizer according to claim 7.   7. The biofertilizer according to claim 6, wherein the biofertilizer is placed in a dormant state by a technique selected from the group consisting of spray drying, refraction-window drying, sun drying, air drying or freeze drying. .   Contains one or more anti-drying additive selected from the group consisting of sorbitol, mannitol, sucrose, sorbitan monostearate, dimethyl sulfoxide, methanol, β-carotene and β-mercaptoethanol to increase post-drying viability The biofertilizer according to claim 6, further comprising a step.   The biofertilizer of claim 6, comprising an additive selected from the group comprising fibrous, cellulosic multi-materials, polymer tackifiers, clays, geotextiles and combinations thereof.   The biofertilizer of claim 6, further comprising a rhizobacteria. Further comprising the absorbed nutrients into biochar, biological fertilizer according to claim 6.